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Dependence of elastic and optical properties on

surface terminated groups in two-dimensional
MXene monolayers: a first-principles study
Cite this: RSC Adv., 2016, 6, 35731
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Yuelei Bai,ab Kun Zhou,*a Narasimalu Srikanth,c John H. L. Pang,a Xiaodong Heb
and Rongguo Wangb

Density functional theory is used to investigate the elastic and optical properties as well as the crystal and
electronic structures of two-dimensional Ti2CT2 and Ti3C2T2 (T ¼ F, O, and OH) MXene monolayers. It is
found that the elastic stiffness, optical response, crystal structure and the electronic structure show
strong dependence on the surface terminated groups often formed with MXene during the etching
process. The elastic stiffness maintains only with the surface termination of O atoms, but a large
degradation is present in the surface terminations of F and OH atoms. The low adsorption and
Received 2nd February 2016
Accepted 4th April 2016
reflectivity in the range from infrared to ultraviolet rays account for the high transmittance of Ti3C2T2
that has been experimentally observed, and it is predicted that Ti2CT2 will have higher optical
DOI: 10.1039/c6ra03090d
transmittance in this range. The calculations also demonstrate the presence of the optical bandgap in
www.rsc.org/advances Ti2CO2, which renders its potential applications in optical and electronic devices.

deposition (CVD),6 which sheds light on the synthesis of other

1. Introduction bare MXenes and opens the door to the understanding of their
Since the discovery of graphene,1,2 studies on two-dimensional fundamental physical properties.
(2D) systems have been extensively conducted because they Originating from the parent MAX phases with different M–X
possess properties signicantly different from those of bulk slabs (n),7 each bare MXene monolayer could have three, ve or
materials. In 2011, a new class of 2D transition-metal carbides seven atomic layers in thickness. In all cases, the thickness of
or nitrides, called MXene,3 was fabricated experimentally by Mn+1XnTx monolayer is less than 1 nm, while the lateral
etching the A-group layer from the transition-metal ternary dimension can reach tens of microns.5 This 2D feature of
layered compounds with the general formula Mn+1AXn (abbre- MXenes inspires some researchers to perform following study
viated to be MAX), where M represents an early transition metal, because in the previous research other 2D materials8 usually
A is an A-group element (mostly groups 13 and 14), X is C or N, exhibit some interesting and unique properties. Since the
and n ¼ 1, 2 or 3.4 Notably, in most cases the etching process potential use as the electrochemical energy storage, such as
with acids or alkalis results in the fabricated MXene usually electrode for batteries, supercapacitors, and hybrid devices was
with some surface terminated functional groups, such as F, O, revealed by Gogotsi et al.,9 some theoretical and experimental
and/or OH.5 Therefore, these terminated MXene species should studies have been extensively performed from pure science to
be referred to as a general formula Mn+1XnTx, where T denotes potential applications,5,10 such as crystal structure,11–13 elec-
a type of surface group (F, OH and/or O) and x is the number of tronic structure,14 elastic properties,15 batteries,16–20 super-
terminations. However, recently a signicant advance has been capacity,21,22 and so on.5,10
made in the synthesis of bare 2D MXene. Bare 2D Mo2C with Considering the fact that more than 60 MAX phases have
high crystallinity, very low defect concentration and no surface been identied and the solid solution of M, A, and/or X sites
terminations was successfully grown by chemical vapour could be formed among the formers,4 it is reasonably expected
that the MXene family should be quite large, and more MXene
phases would be exfoliated from the MAX phases or other
a
School of Mechanical and Aerospace Engineering, Nanyang Technological University, ternary compounds in future. However, to date only some
50 Nanyang Avenue, Singapore 639798, Singapore. E-mail: [email protected]; Fax: selected MXenes were experimentally fabricated, e.g. Ti2C,23
+65 6792 4062; Tel: +65 6790 5499 V2C,19 Nb2C,19 Mo2C,24 Ti3C2,3 Ta4C3,23 Nb4C3,25 (Ti0.5Nb0.5)2C,23
b
National Key Laboratory of Science and Technology on Advanced Composites in (V0.5Cr0.5)3C2,23 Ti3CN.23 Among these MXenes, Ti3C2T2 and
Special Environments and Center for Composite Materials and Structures, Harbin
Ti2CT2 are by far the most studied because they are the earliest
Institute of Technology, Harbin 150080, P. R. China
c
Energy Research Institute @NTU, Nanyang Technological University, 1 CleanTech
identied,3,23 and exhibit many interesting properties that are
Loop, Singapore 637141, Singapore applicable to others in the following studies,5,10 such as

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outstanding intercalation properties with very promising 2. Computational details

applications, including supercapacity21,22 and metal ion
batteries.17,18 All the rst-principles calculations are performed using Vienna
In the past decades, the rapid development of computer Ab-initio Simulation Package (VASP) based on density func-
hardware and computational methods has provided strong tional theory (DFT) where a plane-wave pseudopotential total
tools for the structures and properties of materials at the atomic energy calculation method is employed.32 The plane-wave cutoff
scale, where the rst-principles simulations based on density energy is always set as 520 eV, which is tested to ensure the
functional theory (DFT) have shown the powerful ability to convergence of total energy within 1 meV per atom. Ion-electron
predict and understand the mechanisms of phase stability, interactions are represented by the all-electron projector-
layered structures and unusual properties of the MAX pha- augmented wave (PAW) method,33 with 1s1, 2s22p5, 2s22p2,
ses.7,26,27 It is also true in the eld of MXenes: some important 2s22p4, and 3d24 s2 treated as valence electrons for H, F, O, C,
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issues have been claried or explained using DFT simulations. and Ti, respectively. In addition, the semi-core 3s23p6 states are
For instance, DFT simulations play a crucial role in the struc- treated as valence for Ti elements. The electronic exchange–
tures, properties and potential applications of MXenes.5 In fact, correlation energy (xc) is treated according to the Perdue–
the rst identied multilayer MXene structure—named termi- Burke–Ernzerhof generalized gradient approximations (GGA–
nated Ti3C2T2 layers—was proposed with the support of a DFT PBE)34 and hybrid Heyd–Scuseria–Ernzerhof (HSE06) hybrid
modeling,3 which also helps researchers get some more insights functional.35,36 The latter is constructed by replacing 25% short-
into MXenes as metal ion batteries and other applica- range part of PBE exchange energy (EPBE,SRx ) using a short-range
tions,13,16,18,20,28 and claries why the bare and terminated Ti3C2 Hartree–Fock exchange term (EHF,SRx ), which can be expressed as
MXenes are electronic conductor.14,16 follows:
It is well established that the surface termination on 2D
materials may drastically change the electronic and accompa- EHSE
xc ¼ 0.25EHF,SR
x (m) + 0.75EPBE,SR
x (m)
PBE,LR
nying properties. For instance, alternately hydrogenated and + Ex (m) + EPBE
c (m) (1)
hence fully sp3-bonded graphene, so-called graphene, results in
a fundamental gap at least up to 5.4 eV.29 The similar case is also where EPBE,SR
x is the long-range part of PBE exchange energy,
present in the recently discovered MXenes: their electronic14 and EPBE
c is the PBE correlation energy. The screening parameter
and magnetic30 properties as well as the potential applications m in HSE is always xed as 0.2 Å1. Due to the better perfor-
for metal ion batteries16–20 and supercapacity21,22 are affected mance of HSE06 than PBE in electronic structure (band gap),
greatly by the surface terminations with different functional the former is employed in the calculation of dielectric function.
groups. However, to date there are few reports concerning the The full geometry optimization including the lattice
effect of surface terminated groups on the elastic and optical constants and atomic internal coordinates is conducted using
properties of MXenes. Considering the fact that the derived the conjugate gradient algorithm and 12  12  1 Monkhorst–
MXenes are usually terminated with some surface functional Pack k-point grid which is tested to ensure the total energy
groups like F, O, and OH, it is necessary and timely to perform converged within 1 meV per atom, with the convergence criteria
a systematic study for the dependence of the elastic and optical set such that the difference in total energy is within 1  106 eV
properties on terminated groups. per cell and the force is less than 0.005 eV Å1. A vacuum space
Recently Halim et al.31 reported that about 90% of the light in over 20 Å is added between MXene monolayer and its periodi-
the infrared-to-visible range was transmitted in the epitaxial cally repeated images along c-axis direction of the periodic
Ti3C2Tx lm while it exhibited metallic conductivity down to structure to avoid any interaction. For the density of states
100 K, which indicates that MXenes are promising materials (DOS) and dielectric function of the optimized structure,
for transparent conductive electrode, sensors and so on. To get a much denser k-point mesh of 20  20  1 is used. For the
some more theoretical insights into this issue, the present work Brillouin zone integration, in most cases the rst-order Meth-
is to investigate the optical properties of two typical MXene fessel–Paxton and Gaussian smearing with a width of 0.1 eV are
Ti3C2 and Ti2C using DFT, emphasizing the effect of surface employed for metal and semiconductor (Ti2CO2), respectively,
functional groups. In addition, the elastic stiffness is also where the max entropy term less than 1 meV per atom is ach-
studied. The results show that the optical properties and elastic ieved. However, the tetrahedron method with Blöchl corrections
stiffness of Ti3C2T2 MXenes are both highly dependent on the is employed when calculating DOS.
surface terminated groups, and contribute to understanding The elastic tensor is determined from strain–stress rela-
the experimentally observed high transmittance of Ti3C2T2 tionship by performing six nite distortions of lattice and
MXenes from infrared to ultraviolet rays, and to predicting the deriving the lattice constants.37 The elastic tensor is estimated
higher transmittance in thinner Ti2CT2. The calculations also both, for rigid ions, as well, as allowing for relaxation of the
demonstrate that the optical bandgap is present in Ti2CO2, ions. The ionic contributions are determined by inverting the
which renders it as promising candidate materials in applica- ionic Hessian matrix, which is a matrix of the second derivatives
tions such as the optical and electronic devices. These results of the energy with respect to the atomic positions and here
further indicate that the optical and other properties of Ti2CO2 calculated using nite difference, and multiplying with the
based materials can be tunable by approaches including doping internal strain tensor.38 The convergence criteria for this part is
and solid solution.

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set such that the difference in total energy is within 1  106 eV perpendicular to surface between the topmost and bottommost
per cell, and the force is less than 0.001 eV Å1. atomic layers) are listed in Table 1, including other theoretical
The optical properties of a medium can be fully described by values for comparison. It can be seen that the present data are
the dielectric function, 3(u) ¼ 31(u) + i32(u) at all photon energy well consistent with previous ones.14,15 Comparing with the
u. Aer the electronic ground state has been available, the corresponding MAX (Ti2AlC and Ti3AlC2, Table 1),14 removing Al
dielectric function is estimated in the momentum representa- atoms results in the shrink of a. Moreover, it increases with
tion that needs the matrix elements between occupied and increasing Ti–C slabs in bare and terminated Ti2C and Ti3C2
unoccupied electronic eigenstates. Specically, the imaginary MXenes, e.g. 3.0345 Å in Ti2C and 3.0994 Å in Ti3C2. Upon
part of the dielectric function is determined by a summation termination, a increases in Ti2CT2, but decreases in Ti3C2T2. In
over empty states using the following equation: addition, the O terminated Ti2CT2 and Ti3C2T2 have the lowest
value of a, while a signicantly higher value is present in the F
4p2 e2 X  
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32 ðuÞ ¼ 2 2
knsjpi jkn0 s and OH terminated ones.
Um u 0
knn s The terminated MXenes always have higher Ti(1)–C bond
 0  
 kn sjpi jkns kkn ð1  fkn0 Þdðekn0 ekn  ħu (2) length than bare ones, implying that the interaction between
terminated group T and surface Ti atoms results in the latter
where e, m, U, and fkn are the electron charge, mass, crystal
away from the near C atoms. For both Ti2C and Ti3C2, the
volume, and Fermi distribution, respectively. In addition, |knsi
shortest Ti(1)–T and Ti(2)–C bonds (applicable in Ti3C2), and
represents the crystal wave function corresponding to the nth
longest Ti(1)–C bonds are always present in O terminated
eigenvalue with crystal momentum k and spin s. Since the
MXenes, indicating the strong interaction between O termina-
dielectric constant describes a causal response, the real part
tion and surface Ti atoms. To the contrast, the weak interaction
31(u) is obtained from the imaginary one 32(u) using a Kramers–
could be in the F and OH terminated MXenes that is evidenced
Kronig transformation. Once the dielectric function 3(u) is
in the larger Ti–T bond length. Moreover, for bare and func-
available, the refractivity, reectivity and absorption coefficients
tionalized Ti3C2 except Ti3C2O2, Ti(2)–C bonds are much longer
can be estimated from the standard optical relationships.
than Ti(1)–C bonds, which is common for their parent MAX
phases.7 However, the opposite is present in Ti3C2O2, once
3. Results and discussions again which shows the strong interaction between O termina-
tion and surface Ti atoms.
3.1. Conguration and structural properties
The 2D Ti2CT2 and Ti3C2T2 MXene monolayers are constructed
appropriately by removing Al atoms from their parent MAX 3.2. Electronic structure and chemical bonding
phases, i.e. Ti2AlC and Ti3AlC2.4 With the lowest energy that has The total density of state (TDOS) of bare and terminated Ti2CT2
been revealed in the previous work,11,14,16 the stable congura- and Ti3C2T2 MXene monolayers are shown in Fig. 2. Of most
tions of Ti2CT2 and Ti3C2T2 monolayers are illustrated in Fig. 1, importance, except Ti2CO2 there is a nite DOS value around
where all the functional groups such as F, O, and OH are located the Fermi energy Ef in all Ti2CT2 and Ti3C2T2 monolayers
above the hollow site of three neighboring C atoms, and pointed although it varies with changing functionalized groups, which
to the Ti atoms in the second Ti atomic layer on both sides of indicates that they are all electronic conductors. This is
the MXenes. consistent with the previous theoretical14 and experimental
The in-plane lattice constant a, atomic distance (bond results.3,23 It should be noted that most of MAX phases (the
length) d, and thickness of monolayer L (the distance parent of MXene) also exhibit the electronic conduction
behavior4 because of their metal-like electronic structure.7 It is
shown that Ti2CO2 has a narrow bandgap that is formed by
decreasing Ef (Table 1) upon O termination, indicating it is
semiconductor and could be used for some electronic and
optical devices.
More insights into the electronic structure and chemical
bonding can be gleaned from their partial density of state
(PDOS), as shown in Fig. 2. Clearly, the TDOS at Ef are mainly
attributed to Ti-d electrons and therefore they are involved in
the conduction properties although d electrons are usually
considered not to be efficient conductors, as similar with MAX
phases.7 The lowest valence bands from 12 eV to 10 eV are
formed by the C-s states with a small mixture of Ti-p + d states.
The higher valance bands from 5.5 eV to 2.5 eV in bare Ti2C
and Ti3C2 monolayer correspond to a strong hybridization of T-
d and C-p states (Ti–C bond). However, surface terminations
Fig. 1Side and top views of crystal structures of a 2D Mxene using F, O, or OH group result in a diverge of these bands: the
monolayer: (a) Ti2CT2 and (b) Ti3C2T2. hybridization between p electrons of the terminated atoms and

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Table 1 Lattice constants a, thickness of monolayer L, bond length d, Fermi energy Ef, and elastic constants c11 and c44 of 2D Ti2CT2 and Ti3C2T2
MXenes

a (Å) L (Å) dTi(1)–C (Å) dTi(2)–C (Å) dTi(1)–T (Å) Ef (eV) c11 (GPa) c44 (GPa) Comments

Ti2C 3.0345 2.3046 2.0969 1.5915 609 227

3.007 2.291 636 CASTEP/Wu-Cohen15
Ti2CF2 3.0595 4.7789 2.1013 2.1647 1.4908 391 136
3.0583 4.80 210 2.16 VASP/PBE14
Ti2CO2 3.0329 4.4305 2.1850 1.9726 2.3046 607 212
3.0329 4.45 2.19 1.98 VASP/PBE14
Ti2C(OH)2 3.0717 6.7840 2.1141 2.1791 0.7886 285 111
3.0712 6.79 2.12 2.18 VASP/PBE14
0.4446
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Ti3C2 3.0994 4.6320 2.0496 2.2216 491 206

3.071 4.605 523 CASTEP/Wu-Cohen15
Ti3C2F2 3.0777 7.2160 2.0734 2.1936 2.1744 0.4202 436 166
3.0775 7.21 2.08 2.17 CASTEP/Wu-Cohen15
Ti3C2O2 3.0393 6.9592 2.1932 2.1582 1.9755 1.3124 523 191
Ti3C2(OH)2 3.0874 9.2170 2.0848 2.1949 2.1904 1.5409 341 137
Ti2AlC 3.0687 VASP/PBE14
Ti3AlC2 3.0816 VASP/PBE14

d electrons of surface Ti atoms makes some bands move into the underestimation of the r values and elimination of the A
lower energy range, which corresponds to the Ti-T bond; the layers that is also evidenced in the shrink of in-plane lattice
hybridization states between Ti-d and C-p states shi slightly to constant,15 but surface termination using other functional
higher energy range. In the OH terminated MXenes, the peak groups results in a decrease of elastic stiffness, where the lowest
around 10 eV corresponds to the hybridization between H-s values are present in OH terminated ones, and the degradation
and O-p states with the minor mixture of O-s states (H–O of elastic stiffness is more in Ti2CT2 than Ti3C2T2. Although cij
bond). Although the decreasing Ef (Table 1) upon O termination of the bare and O terminated MXenes decreases with increasing
is also present in functionalized Ti3C2 MXenes, no bandgap is Ti–C slabs, an opposite trend is observed in the F and OH
observed between two related bands mainly because of the terminated ones.
widening of Ti-d states, which is related to the fact that all Ti3C2 Due to the similar bond length of Ti–C in the terminated
MXenes are electronic conductors. In addition, in Ti2CO2 and MXenes, it is reasonable that the Ti–C bond strength should not
Ti3C2O2 some hybridization states between Ti-d and O-p elec- change a lot with the termination of functional group. It follows
trons with a mixture of minor O-s electrons are present in the that the key factor for elastic stiffness is the bonding strength
much lower energy range around 18.5 eV (not shown in between the bare MXenes and terminated groups. As shown in
gure), which indicates the strong coupling between surface Table 1, the much larger change of Ti–C bond length in the O
terminated O atoms and bare MXenes, and contributes to the terminated Ti2CT2 and Ti3C2T2 indicates the strongest coupling
lowest Ef for Ti2CO2 (2.3046 eV) and Ti3C2O2 (1.3124 eV). between O atoms and bare MXenes, which is also supported by
examining PDOS of Ti2CO2 and Ti3C2O2 (Fig. 2). Although the
3.3. Elastic stiffness change of Ti–C bond length is comparable in F and OH termi-
nations, the associated increase of layer thickness (Table 1) is
Consistent with the previous work on MXenes by Kurtoglu much less in the former than later, which results in the lowest
et al.,15 the elastic constants in-plane cij are calculated using elastic stiffness of OH terminated MXene monolayers.
following expression:
3.4. Dielectric function and optical properties
cij ¼ cij,cell(c/r) (3)
To investigate the optical properties of MXenes, we have
where cij,cell is the elastic constant directly calculated in a unit calculated the imaginary part (32) of the dielectric function
cell including a vacuum space between two monolayers, and r is against photon frequency along in-plane and out-plane direc-
the thickness of the MXene monolayer which is dened as the tions, as displayed in Fig. 3. Of most importance, the optical
distance between the topmost surface layers, for simplicity and bandgap is present only in Ti2CO2 because of its
clarity. semiconductor-like electronic structure in origin (Fig. 2).
The calculated elastic constants c11 and c44 of Ti2CT2 and Notably, the present optical bandgap, around 1 eV, is much
Ti3C2T2 monolayers are listed in Table 1. They are well consis- higher than the bandgap from DOS in Fig. 2 (around 0.3 eV).
tent with the previous theoretical values of bare Ti2C and Ti3C2 The reason is that on the one hand, Ti2CO2 has an indirect
monolayers by other researchers.15 Of most importance, cij bandgap where interband transition needs lager energy because
strongly depends on the terminated functional groups: cij of the of the different crystal momentum between minimal-energy
bare and O terminated MXenes have very high stiffness (over state in the conduction band and the maximal-energy state of
490 GPa of c11 and around 200 GPa of c44) probably because of the valence band; one the other hand, PBE usually

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Fig. 2 (TDOS) and (PDOS) of 2D Mxene monolayer Ti2CT2 and Ti3C2T2. The Ti-s and T-p states are not illustrated due to the limited space
although they are also contributed to some valance bands. The Fermi energy is always set to 0 eV, and marked in dot-dash red line vertically.

underestimates the bandgap than the more accurate HSE06 low-energy region. Very interestingly, a optical bandgap is
that is used in the calculation of dielectric function.14 present in the out-plane direction (32,zz) even in the metal-like
Similar with electronic structure and elastic constants, 32 is Ti2CF2 and Ti3C2O2, while for Ti2CO2 it is also widen to 2.3
strongly dependent on the terminated surface groups. And due eV, which is attributed to their anisotropic electronic structure
to the anisotropic crystal structure, the corresponding aniso- and chemical bonding (valence bonds). In addition, 32 in the F
tropic dielectric function is observed that 32 is different along terminated MXenes exhibits similar behavior with OH termi-
in-plane (32,xx) and out-plane (32,zz) directions, especially in the nated ones, which originates from their similar electronic

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Fig. 3 Imaginary part of the in-plane (32,xx) and out-plane (32,zz) dielectric function as a function of photon frequency for (a) functionalized Ti2CT2
and (b) Ti3C2T2 monolayer.

structure (TDOS, Fig. 2). Moreover, 32,xx in the O terminated In practice, the experimentally obtained optical properties
MXene is very low below around 1 eV, and increases quickly are usually the adsorption coefficients a and refractivity R.
with increasing photon frequency, peaking at a frequency (2–4 Therefore, the in-plane and out-plane a and R are estimated
eV), while upon other terminations a much higher 32,xx value is from the calculated dielectric function as a function of
present in the low-frequency range. Notably, 32,xx is much lower frequency, as illustrated in Fig. 4 and 5, respectively. Consid-
in F and OH terminated MXenes than the others in a narrow ering the anisotropic dielectric function, it is not surprising to
range for Ti2CT2 (1.4–6.5 eV) and Ti3C2T2 (1.4–4.5 eV), while it is obtain anisotropic a and R in the bare and terminated Ti2CT2
not true for 32,zz. and Ti3C2T2. As a semiconductor, Ti2CO2 almost can not adsorb
It should be noted that the interband transition that is any light below about 1 eV in plane and 2.3 eV out plane, where
treated in the DFT simulation is much less important than it reects only about 12% and 6% light, respectively. The zero
intraband transition in the low energy (<1 eV) for metal. The adsorption and low refractivity are also present in out-plane
latter is the dominant mechanism in low energy of metal and direction of Ti2CF2 and Ti3C2O2. In the range from near-
metal-like materials, and should be expressed using empirical infrared to ultraviolet [Ti2CT2 (1.4–6.5 eV) and Ti3C2T2 (1.4–4.5
Drude term, which can be written as the dielectric function: eV)] including visible light, the in-plane adsorption coefficients
axx is signicantly lower in the F and OH terminated MXenes
up 2
3D ðuÞ ¼ 1  (4) than the bare and O terminated ones, of more importance, with
uðigD þ uÞ
the low refractivity, where the axx and Rxx both change very
here, up is the plasma frequency and gD is the damping slightly with increasing frequency. This indicates that the pure
parameter. Both up and gD depend on many details of the F and OH terminated Ti2CT2 and Ti3C2T2 should exhibit white
material and usually is obtained from experiment, and they colour. Moreover, overall Ti3C2T2 has the higher Rxx value than
describe the broadening of the spectra due to effects not Ti2CT2, which shows that increasing Ti–C slabs or thickness of
included in the DFT calculation. For examples, processes of monolayer can result in the increase of Rxx. It should be noted
electron–electron scattering (including Auger processes), that due to the metal-like electronic structure, their parent MAX
electron-phonon scattering, and electron-defect scattering phases always have relative strong adsorption without optical
could contribute to the broadening. And the last contribution bandgap compared with MXenes,27,39 while R is much higher in
usually plays the most important role. Although eqn (4) is valid the former than the latter especially in the low energy range. In
for all frequencies, in practice it is signicant only in the low- other words, MAX phases are always lighttight, which has been
energy infrared part of the spectra (usually <1 eV) and can be conrmed in previous experiments,40 but in some MXenes like
neglected in the high frequency. This means the larger imagi- Ti2CO2 the light can be transmitted.
nary part of the dielectric function in low energy <1 eV when In the previous work, the recent experimental research on
considering the intraband transition, and strong optical the optical properties of Ti3C2T2 (ref. 31) shows that more than
adsorption in practice for the bare and terminated Ti2CT2 and 90% light could be transmitted in a single MXene layer, with the
Ti3C2T2 except Ti2CO2. slight change against photon energy. It is well known that light

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Fig. 4 In-plane (axx) and out-plane (azz) adsorption coefficient as a function of photon frequency for (a) functionalized Ti2CT2 and (b) Ti3C2T2
monolayer.

Fig. 5 In-plane (Rxx) and out-plane (Rzz) reflectivity as a function of photon frequency for (a) functionalized Ti2CT2 and (b) Ti3C2T2 monolayer.

is electromagnetic wave where the electric and magnetic elds 90% from infrared to ultraviolet rays is observed in the experi-
of lights are both perpendicular to each other and perpendic- ment. Moreover, based on the prediction that the much lower
ular to the direction of energy and wave propagation. This Rxx and monolayer thickness are present in F and OH termi-
means that the photos react with MXenes in plane when a light nated Ti2CT2 (2–4%) than Ti3C2T2 (6–10%) (Fig. 5), it is
shines perpendicularly on it, as in ref. 31. And the recent reasonable to assume that the former should have higher
experimental result41 indicates that MXenes have a surface optical transmittance.
termination layer that is a mixture of OH and F mainly. Clearly, Notably, as a semiconductor, Ti2CO2 has very different
the low axx and Rxx of F and OH terminated Ti3C2T2 (Fig. 4 and electronic structure and optical properties, which renders it for
5) monolayers are the reason why the high transmittance at over applications in the electronic and optical devices. It is inspired

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that the pure Ti2CO2 would be synthesized and optically char- 4 M. W. Barsoum, Prog. Solid State Chem., 2000, 28, 201–281.
acterized in future. In addition, for these potential applications 5 M. Naguib, V. N. Mochalin, M. W. Barsoum and Y. Gogotsi,
the electronic structure and optical properties of Ti2CO2-based Adv. Mater., 2014, 26, 992–1005.
materials can be further tuned by doping or solid solution. 6 C. Xu, L. Wang, Z. Liu, L. Chen, J. Guo, N. Kang, X.-L. Ma,
H.-M. Cheng and W. Ren, Nat. Mater., 2015, 14, 1135–1141.
4. Conclusions 7 Y. L. Bai, X. D. He, R. G. Wang, S. Wang and F. Y. Kong,
Comput. Mater. Sci., 2014, 91, 28–37.
The bare and terminated Ti2CT2 and Ti3C2T2 (T ¼ F, O, and OH) 8 V. Nicolosi, M. Chhowalla, M. G. Kanatzidis, M. S. Strano and
MXene monolayers are investigated using rst principle calcu- J. N. Coleman, Science, 2013, 340, 1420.
lations, emphasizing the elastic and optical properties with 9 M. R. Lukatskaya, O. Mashtalir, C. E. Ren, Y. Dall'Agnese,
their dependence of surface terminated groups. The surface P. Rozier, P. L. Taberna, M. Naguib, P. Simon,
Published on 05 April 2016. Downloaded by Brown University on 02/05/2016 08:37:14.

terminated groups have a signicant effect on the crystal M. W. Barsoum and Y. Gogotsi, Science, 2013, 341, 1502–
structure, electronic structure, chemical bonding, elastic prop- 1505.
erties, and optical properties. Surface termination results in the 10 J. C. Lei, X. Zhang and Z. Zhou, Front. Phys China, 2015, 10,
shrink in Ti2CT2 and expansion in Ti3C2T2 of the in-plane lattice 276–286.
constant, where the largest change is present in O terminated 11 A. N. Enyashin and A. L. Ivanovskii, Comput. Theor. Chem.,
ones. Correspondingly, the elastic stiffness maintains only in 2012, 989, 27–32.
Ti2CO2 and Ti3C2O2 that is also evidenced from their electronic 12 C. Y. Shi, M. Beidaghi, M. Naguib, O. Mashtalir, Y. Gogotsi
structure: some hybridization states between Ti and O atoms and S. J. L. Billinge, Phys. Rev. Lett., 2014, 112, 5.
are in a much lower energy range around 18.5 eV, but this is 13 X. F. Wang, X. Shen, Y. R. Gao, Z. X. Wang, R. C. Yu and
not true with the other terminations. The anisotropic optical L. Q. Chen, J. Am. Chem. Soc., 2015, 137, 2715–2721.
properties using hybrid functional HSE06 against photon 14 Y. Xie and P. R. C. Kent, Phys. Rev. B: Condens. Matter Mater.
frequency, including dielectric function, adsorption coefficients Phys., 2013, 87.
and reectivity, strongly depend on surface terminated groups. 15 M. Kurtoglu, M. Naguib, Y. Gogotsi and M. W. Barsoum,
The optical bandgap is present only in Ti2CO2, originating from MRS Commun., 2012, 2, 133–137.
its semiconductor-like electronic structure, which renders its 16 Q. Tang, Z. Zhou and P. W. Shen, J. Am. Chem. Soc., 2012,
potential applications in optical and electronic devices. More- 134, 16909–16916.
over, for these potential applications the optical and other 17 O. Mashtalir, M. Naguib, V. N. Mochalin, Y. Dall'Agnese,
properties of Ti2CO2-based materials can be further tunable by M. Heon, M. W. Barsoum and Y. Gogotsi, Nat. Commun.,
the approaches including doping and solid solution. With the 2013, 4.
surface termination of F and OH functional groups, the low 18 Y. Xie, M. Naguib, V. N. Mochalin, M. W. Barsoum,
adsorption and reectivity from infrared to ultraviolet rays Y. Gogotsi, X. Q. Yu, K. W. Nam, X. Q. Yang,
account for the high transmittance of Ti3C2T2 that is observed A. I. Kolesnikov and P. R. C. Kent, J. Am. Chem. Soc., 2014,
in experiments, and it is predicted that the thinner Ti2CT2 136, 6385–6394.
monolayer should have higher optical transmittance. 19 M. Naguib, J. Halim, J. Lu, K. M. Cook, L. Hultman,
Y. Gogotsi and M. W. Barsoum, J. Am. Chem. Soc., 2013,
Acknowledgements 135, 15966–15969.
20 C. Eames and M. S. Islam, J. Am. Chem. Soc., 2014, 136,
The authors acknowledge nancial support from Ministry of 16270–16276.
Education, Singapore (Academic Research Fund TIER 1 – 21 M. Ghidiu, M. R. Lukatskaya, M. Q. Zhao, Y. Gogotsi and
RG128/14). YB gratefully acknowledges the support from M. W. Barsoum, Nature, 2014, 516, 78–U171.
National Natural Science Foundation of China (Grant No. 22 Y. Dall'Agnese, M. R. Lukatskaya, K. M. Cook, P. L. Taberna,
11302061) and International Postdoctoral Exchange Fellowship Y. Gogotsi and P. Simon, Electrochem. Commun., 2014, 48,
Program by the Office of China Postdoctoral Council (Grant No. 118–122.
20130004). 23 M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu,
L. Hultman, Y. Gogotsi and M. W. Barsoum, ACS Nano,
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